Phosphorus-containing duromers of oligophosphites

ABSTRACT

This invention relates to new phosphorus-containing duromers of oligophosphites and epoxides or bisacrylates or unsaturated polyesters.

The invention relates to new phosphorus-containing duromers ofoligophosphites and epoxides or bisacrylates or unsaturated polyesters.

The reaction of spiro-bisphosphites containing phosphorous acidtriesters groups with epoxy resins has been disclosed in EP-A 420 811.Brownish, duromeric moulding compounds were obtained.

The reaction of unsaturated compounds with diphosphites (diesters ofphosphorous acid) for the preparation of polymers is known in principle.

Thus U.S. Pat. No. 31 94 795 teaches the preparation of a cyclicphosphite from trimethylolpropane monoallylether with triphenylphosphitefollowed by saponification of the cyclic triester and the polymerisationof this compound. A disadvantage of this process is that the reactionmust be carried out in two stages in order to avoid the simultaneouspresence of phosphorus-hydrogen bonds and allyl groups at elevatedtemperatures (spontaneous decomposition).

U.S. Pat. No. 31 58 642 describes the preparation of polyphosphineoxides from phenylphosphine and alkynes. Phenylphosphine is inflammableand the handling of alkynes at elevated temperatures under pressure isdifficult.

The reaction of phosphorus-hydrogen bonds with unsaturated groups oftensioned small rings is of interest in spite of these difficulties asit enables duromers varying from rubber-like systems to rigid,flame-resistant materials to be obtained according to the choice of thestarting materials. It would therefore be desirable to use startingmaterials which are readily synthesized and safe to handle.

It has now been found that mixtures of oligophosphites and unsaturatedcompounds of mixtures of oligophosphites and epoxides harden to formduromers.

The present invention therefore relates to duromers which are obtainableby the reaction of

A) oligophosphites corresponding to formula I ##STR1## wherein R denotesa C₂ -C₄₄ -alkylene group or corresponds to formula (II), (IV) or (V)##STR2## Ar stands for a C₆ -C₁₄ arylene group or corresponds to formula(III) ##STR3## wherein R¹ stands for a C₁ -C₄ -alkyl group or hydrogenand the groups R¹ may be identical or different.

R² stands for a C₁ 14 C₁₂ -alkylidene, a C₆ -C₁₂ -cycloalkylidene, a C₂-C₂₀ -alkylene, an araliphatic, divalent C₇ -C₂₆ group, an oxygen atom,a carbonyl group, a sulphur atom, a sulphone group or a chemical bond.

X stands for a C₁₋ C₄ -alkyl group,

m and p stand for natural numbers from 1 to 200 and

n stands for a natural number from 1 to 20,

or of oligophosphites obtainable by the reaction of dimethylphosphite ordiethylphosphite or dipropylphosphites or dibutylphosphites with triols,each of which has two OH groups in the 1,2- or 1,3-position, optionallytogether with diols whose organic residue has the meaning of R or R¹,the oligophosphites thus obtained containing structural unitscorresponding to formulae (VI), (VII), (VIII) or (IX) ##STR4## and R³denotes a C₁ C₁₂ -alkylene group with

B1) polyunsaturated units such as, for example, unsaturated polyesterspreferably containing maleic acid or fumaric acid ester units or allylether group-containing units as unsaturated units or acrylates ormethacrylates of di- or polyols, or by the reaction of oligophosphites Awith

B2) di- or polyfunctional epoxides,

from 0.7 to 5 equivalents of double bonds or epoxy groups being used foreach phosphite equivalent.

The invention further relates to a process for the preparation of theduromers according to the invention, characterised in that the mixturesof oligophosphite A and polyunsaturated units B1) are hardened with from0 to 5% by weight of basic catalysts such as hydroxides, carbonates orC₁ -C₅ -alcoholates of alkali metals or alkaline earth metals or with 0to 5% by weight of initiators for radical reactions such as azocompounds or peroxy compounds, the basic catalysts being effective onlyfor unsaturated polyesters containing maleic acid or fumaric acid esterunits, or the mixtures of oligophosphites A) and epoxides B2) arehardened with from 0 to 5% by weight of basic catalysts such ashydroxides, carbonates or alcoholates of alkali metals or alkaline earthmetals, hardening being carried out at temperatures from 80° C. to 220°C. for 0.1 to 10 hours.

The invention also relates to oligophosphites obtained by the reactionof diols whose organic residue has the meaning of R or R¹ with from twoto ten times the molar quantity of dimethylphosphite, diethylphosphite,dipropylphosphites or dibutylphosphites in the presence of from 0.01 to2% by weight of basic catalysts, preferably alkali metal carbonates, motpreferably potassium carbonate. In this reaction, the aliphatic alcoholswhich are formed from the dialkylphosphites are first distilled off attemperatures from 100° to 190° C., preferably at normal pressure, anddialkylphosphite is then distilled off at temperatures from 100° to 190°C., preferably at a reduced pressure of from 1 to 100 mbar.

The invention further relates to oligophosphites obtained by therreaction of dimethylphosphite or diethylphosphite or dipropylphosphitesor dibutylphosphites with triols having in each case two OH groups inthe 1,2- or 1,3-positions to one another, optionally together with from0 to 10 mol of diols, based on 1 mol of triol, the organic residues ofwhich diols have the meaning of R and R¹, in the presence of from 0.01to 2% by weight of basic catalysts, preferably alkali metal carbonates,most preferably potassium carbonate, the aliphatic alcohols formed fromthe dialkyl phosphites being first distilled off at temperatures from100° to 190° C., preferably at normal pressure, and the dialkylphosphitebeing then distilled off at temperatures from 100° to 190° C.,preferably at a reduced pressure of from 1 to 100 mbar, the molar ratioof diphosphite to the sum of triols+diols being from 10:1 to 3:1.

The epoxides used according to the invention are known and are describede.g. in Houben-Weyl, Methoden der organischen Chemie,Georg-Thieme-Verlag 1987, Volume E20/Part 3, pages 1891 to 1993.Glycidyl ethers of di- or polyphenols are preferred, e.g. glycidylethers of Novolaks.

The unsaturated polyesters used according to the invention are known andare described e.g. in Houben-Weyl, Methoden der organischen Chemie,Georg Thieme Verlag 1987, Volume E20/Part 2, pages 1414 to 1418. Maleicacid anhydride, fumaeric acid, neopentyl glycol, adipol, butyleneglycol, ethylene glycol, diethylene glycol, phthalic acid anhydride,trimethylolpropane, propylene glycol, trimethylolpropane diallyletherand adipic acid are preferred compounds for the polyester used accordingto the invention; at least one of the components present must beunsaturated.

The acrylates or methacrylates of di- or polyols used according to theinvention are bisacrylates or bismethacrylates of adipol, diethyleneglycol, butylene glycol or ethylene glycol or the triascrylates ortrismethacrylates of trimethylolpropane or the tetrakisacrylates ortetrakismethacrylates of pentaerythritol.

The oligophosphites according to the invention are easy to prepare andsafe owing to the moderate temperatures at which they are prepared.

The process according to the invention for the preparation of theduromers proceeds without any liberation of volatile by-products.

The duromers according to the invention are suitable for the productionof optical articles such as optical fibres, elastomers and all productsfor which duromers are normally used.

EXAMPLES Preparation Of The Phosphites Example 1a

200 g of 2,2-bis-(4-hydroxyethyloxyphenyl)-propane (Dianol-22) are mixedwith 200 g of diethylphosphite and 1 g of potassium carbonate. Themixture is heated to 160° C. for 6 hours, during which time ethanoldistils off, among others. A water jet vacuum is then applied and theresidue is heated to 120° C. for 2 hours, during which diethylphosphitedistils off. 241 g of oligophosphite are obtained.

Example 2a

500 g of Polyethylene glycol having a molar mass of 400 g/mol are mixedwith 300 g of diethylphosphite and 2 g of potassium carbonate. Themixture is heated to 160° C. for 6 hours, during which time ethanoldistils off, among others components. A water jet vacuum is then appliedand the residue is heated to 120° C. for 2 hours, during whichdiethylphosphite distils off. 585 g of oligophosphite are obtained.

Example 3a

1000 g of Polytetrahydrofuran having a molar mass of 2000 g/mol aremixed with 300 g of diethylphosphite and 4 g of potassium carbonate. Themixture is heated to 160° C. for 6 hours, during which time ethanoldistils off, among others components. A water jet vacuum is then appliedand the residue is heated to 120° C. for 2 hours, during whichdiethylphosphite distils off. 1090 g of oligophosphite are obtained.

Example 4a

135 g of Trimethylolpropane are mixed with 420 g of diethylphosphite and2 g of potassium carbonate. The mixture is heated to 160° C. for 6hours,during which ethanol distils off, among other components. A water jetvacuum is then applied and the mixture is heated to 120° C. for 2 hours,during which diethylphosphite distils off. 199 g of oliogophosphiteswhich may be branched and/or contain cyclic groups ar obtained.

Preparation Of The Unsaturated Polyester Used Example 1b

173 g of Dimeric fatty acid, 294 g of maleic acid anhydride, 212.4 g ofadipol, 187.2 g of neopentyl glycol, 0.3 g of dibutyl tin oxide and 0.6g of hydroquinone are mixed together. The mixture is heated to 120° C.for 30 minutes, to 160° C. for 1.5 hours and to 210° C. for 4.5 hours.Water distils off in the process, among other components. 722 g ofunsaturated polyester are obtained.

Preparation OF The Duromers Example 1c

10 g of the Oligophosphite from Example 1a are mixed with 10 g ofunsaturated polyester from Example 1b. The mixture is heated to 180° C.for 3 hours, 50 mg of a 30% sodium methanolate solution in methanol areadded and the mixture is heated to 180° C., for 5 hours. A vitreous,insoluble mass having a glass temperature of 11° C. and a decompositiontemperature of 369° C. (maximum of decomposition) is obtained.

Example 2c

10 g of the Oligophosphite from Example 1a are mixed with 6 g of adipolbisacrylate and the mixture is heated to 50° C. 0.5 g of Trigonox B(initiator of Akzo Company) is added and the mixture is then heated to100° C., for 0.5 hours and to 170° C. for 2 hours. An opaque, whiteduromer mass having a glass temperature of 22° C. and a decompositiontemperature of 361° C. (maximum of decomposition) is obtained.

Example 3c

10 g of the Oligophosphite from Example 2a are mixed with 10 g ofAraldite PY 307 (Novolak epoxide of Ciba Company) and the mixture isheated to 160° C. 50 mg of 30% solution of sodium methanolate inmethanol are added and the mixture is heated to 160° C., for one hour. Afurther 50 mg of the sodium methanolate solution is added and theresulting mixture is heated to 160° C. for 30 minutes. A rubber-like,transparent mass having a glass temperature of -21° C. and adecomposition temperature of 345° is obtained.

We claim:
 1. Duromers obtainable by the reaction ofA) oligophosphitescorresponding to formula I ##STR5## in which R stands for a C₂ -C₄₄-alkylene group or corresponds to formula (II), (IV) or (V) ##STR6## Arstands for a C₆ -C₁₄ -arylene group or corresponds to formula (III)##STR7## wherein R¹ stands for a C₁ -C₄ -alkyl group or for hydrogen andthe groups denoted by R¹ may be identical or different,R² stands for aC₁ -C₁₂ -alkylidene, a C₆ -C₁₂ -cycloalkylidene or a C₂ -C₂₀ -alkylenegroup or an araliphatic, divalent C₇ -C₂₀ -alkylene group oranaliphatic, divalent C₇ -C₂₆ -group, an oxygen atom, a carbonyl group,a sulphur atom, a sulphone group or a chemical bond, X stands for a C₁-C₄ -alkyl group, m and p stand for natural numbers from 1 to 200 and nstands for a natural number from 1 to 20, or of oligophosphites obtainedby the reaction of dimethylphosphite or diethylphosphite ordipropylphosphites or dibutylphosphites with triols in which two OHgroups are in each case the 1,2- or 1,3-position to one another,optionally with the addition of diols whose organic residue correspondsto R or R¹, the oligophosphites thus obtained containing structuralunits corresponding to formulae (VI), (VII), (VIII) or (IX) ##STR8## andR³ corresponds to a C₁ -C₁₂ -alkylene group with B1) polyunsaturatedunits such as unsaturated polyesters containing maleic acid or fumaricacid ester units or allyl ether group-containing units as theirunsaturated units, or acrylates or methacrylates of diols or polyols, orby the reaction of oligophosphites A with B2) difunctional orpolyfunctional epoxides,from 0.7 to 5 equivalents of double bonds orepoxy groups being used for each phosphite equivalent.
 2. A process forthe preparation of the duromers according to claim 1, characterised inthat the mixtures of oligophosphite A and polyunsaturated units B1) arehardened with from 0 to 5% by weight of basic catalysts such ashydroxides, carbonates or C₁ -C₅ -alcoholates of alkali metals oralkaline earth metals or with from 0 to 5% by weight of initiators forradical reactions such as azo compounds or peroxy compounds, the basiccatalysts being effective only for unsaturated polyesters having maleicacid or fumaeric acid ester units, or the mixtures of oligophosphites A)and epoxides B2) are hardened with from 0 to 5% by weight of basiccatalysts such as hydroxides, carbonates or alcoholates of alkali metalsor alkaline earth metals, hardening being carried out at 80° C. to 220°C. for 0.1 to 10 hours.